Azo dyes



Patented Feb. 21, 1939 UNITED STATES PATENT OFFICE AZO DYES Swanie S. Rossander, Wilmington, Del., assignor to E. I. du Pont de Nemours & Company, Wilmington, Del., a corporation of Delaware Application January 23, 1937,

N Drawing.

Serial N0. 122,011

8 Claims.

scribed with reference to particular examples but this description is to be taken as exemplary, not limitative.

B. It is an object of the invention to dye cotton and regenerated cellulose particularly, and also wool, leather, and organic derivatives of cellulose, such as the cellulose esters and ethers, by

amine, and aceto acetanilide. The objects of the invention are accomplished in a preferred form by dyeing the material with the products of the said identified application, subjecting the dyed fiber to a diazotization process and coupling it to the selected developing agent. Preferred results are sometimes obtained by the use of beta naphthol and l-phenyl-3-methyl-5-pyrazolone. It will be found that dyestufis possessing ortho amino azo groups on the N components are not generally diazotizable and are, consequently, not satisfactory for use in this invention.

D. The invention will be more fully comprehended by reference to the examples, in the table of which the arrows indicate that the preceding compound is diazotized and coupled to the indicated equivalents of the compounds to which the arrows point. The symbol PAB means paraamino-benzoyl and the symbol MAB means metaamino-benzoyl.

Example I Five parts of cotton piece goods were dyed in the usual manner known to those in the art with ten-hundredths part of (l-meta-amino-phenyl- 3 methyl--pyraz01one)2ZDi (para-amino-benzoyl) 1:3-diamino benzenel-sulfonic acid. The dyed fabric (yellow in color) was rinsed in cold water and put in a casserole with 200 parts of water at 20 C. Three-tenths part of sodium nitrite and four-tenths part of sulfuric acid were added. The whole was stirred 15 minutes and rinsed with cold water. One-tenth part of 1- phenyl-3-methyl-5-pyrazolone was dissolved in 200 cc. water and one-tenth part of soda ash. The solution was stirred rapidly while adding the above rinsed piece goods and then stirred slowly for 15 minutes and rinsed in cold water and dried. The dyeing was a bright greenish yellow in shade. The formula of the dye on the fiber is:

0 0 N S OaNB \N/ Example II Five parts of cotton piece goods were dyed in the usual manner known to those skilled in the art with two hundredths part of di(para amino benzoyl) meta phenylene diamineZU-acid) 2. The dyed fabric (red in color) was rinsed in cold water and put in a casserole with 200 parts of water at 20 C. Three tenths part of sodium nitrite and four tenths part of sulfuric acid were added. The whole was stirred 15 minutes and rinsed with cold water. One tenth part of 2- naphthol was dissolved in 200 parts of water and one twentieth part of caustic soda. The solution was stirred rapidly while adding the above rinsed piece goods. The mass was stirred for 15 minutes; rinsed in cold water and dried. The

Etssu JUN 4 19 dyeing was a bright Bordeaux shade. The formula of the dye on the fiber is:

SOsNa Example III Five parts of cotton piece goods were dyed in the usual manner known to those skilled in the art with two hundredths part of di meta amino benzoyl 1 3 diamino benzene 4 sulfonic acid3(meta amino benzoyl J-acid) 2. The dyed fabric (orange in color) was rinsed in cold water and put in a casserole with 200 parts of water at 20 C. Three tenths part of sodium nitrite and S OaNa NHCO of water at 20 C. Three tenths part of sodium nitrite and four tenths part of sulfuric acid were added. The whole was stirred 15 minutes and rinsed with cold water. One tenth part of 2- naphthol was dissolved in 200 parts of water and one-twentieth part of caustic soda. The solution was stirred rapidly while adding the above rinsed piece goods. The mass was stirred for 15 minutes, rinsed in cold water and dried. The dyeing was a bright yellow orange shade; The formula of the dye on the fiber is:

' some Example V 8 parts of (1-meta-amino-phenyl-3-methyl-5- pyrazolone) 2;di(para amino benzoyl) 1:3 diamino benzene-'i-sulfonic acid were slurried with 300 parts of water. 2 parts of caustic soda were added and warmed to solution and then cooled to 20 C. 2 parts of sodium nitrite were added and the whole was dumped in 5 parts of hydrochloric acid and stirred for 3 hours, maintaining CONE- NaOsS NHCO S OsNa Example IV Five parts of cotton piece goods were dyed in the usual manner known to those skilled in the art with two hundredths part of di(para amino benzoyl) l-3-diamino benzene-4-sulfonic acid 3 (l-meta amino phenyl-3-methyl-5-pyrazolone)z. The dyed fabric (yellow in color) was rinsed in cold water and put in a casserole with 200 parts acidity to Congo red and a distinct excess of sodium nitrite.

5 parts of beta naphthol were slurried with 200 parts of water. Approximately 1.4 parts of caustic soda were added and warmed to solution, distinctly alkaline to brilliant yellow paper. The whole was cooled to 20 C. 10 parts of soda ash were added and stirred until dissolved. The

tetrazo prepared in the above paragraph was.

NaOzS SOzNa -100 C. The dried powder was yellow. The formula of the dye is:

Example VI 11 parts of (para-amino-benzoyl J -acid)2Z di (para-amino-benzoyl) 1:3-diamino benzene-4- sulfonic acid were slurried with 300 parts of water. 2 parts of caustic soda were added and warmed until dissolved. The whole was cooled to 20 C. and 2 parts of sodium nitrite were added. The mass was dumped in 5 parts of hydrochloric acid and stirred for 3 hours, maintaining an acidity to Congo red and distinct excess of sodium nitrite.

5 parts of 1-phenyl-3-methyl-5-pyrazolone soda were slurried and stirred at 20 C. until dissolved. 10 parts of soda ash were added and stirred until dissolved. The tetrazo prepared in the above paragraph was slowly added. The mass was CONH stirred 3' hours, keeping an excess of 1-phenyl-3- methy1-5-pyrazolone and red alkalinity on brilliant yellow paper. The mass was warmed to 70 C., filtered, and dried at 90-100 C. The formula of the dye is:

S OaNa N=NO0 o mar- Example VII Five parts of cotton piece goods were dyed in S OaNa the usual manner known to those in the art with four-hundredths part of (para-amino-benzoyl Jacid)z :di (para-amino-benzoyl) 1:3-diamino benzenei-sulfonic acid. The dyed fabric (orange in shade) was rinsed in cold water and put in a casserole with 200 parts of water at 20 C. Threetenths part of sodium nitrite and four-tenths part of sulfuric acid were added. The whole was stirred 15 minutes and rinsed with cold water. One tenth part of 2 naphthol was dissolved in 200 parts water and one twentieth part of caustic soda. The solution was stirred rapidly while adding the above rinsed piece goods. The mass was stirred for 15 minutes, rinsed in cold water and dried. The dyeing was a bright orange shade. The formula of the dye is:

N=NOC ONH ty I OaNa I In the following tables precedm'es similar to pling components comprise benzene, naphthathe foregoing were employed. I lene, pyrazelones, quinoline or aceto acetanfllde Diazo component 7 Coupling component Shade on cotton 5 Orange. 8 D1(para-ammo-benzoyl) 1:3-d1amxno benzene Scarlet.

o. Meta tolylene diamine. Dull scarlet.

2:4-dihydroxy quinoline Orange. 9 D1(para-ammo-benzoyl) 1:3-d1am1no benzene 10' 3((meta-aminwbenzoyl) I-nvidh Beta naphthol 10 Di( para-aminobenzoyl) 1:3-diamino benzene jog ----dO 1 011168111. 11 Di(para-amino-benzoyl) 1:3-diamino benzene Orange I5 3(l-meta-amino-phenyl-5-pyrazolone-3-carboxylieacid): l-phenyl-Ii-methyl-5-pyrazolone Yellow.

Beta naphthol Orange. 12 Di(para-amino-benzoyl) 1:3-diamino benzene 1-phenyl-3-methyl-5-pyrazolone Yellow.

-)((para-emlno-benzoyl) .T-aoid) (l-meta-amino-pheny1-5-pyrazolone-3- 2-4 dihydroxy quinoline Do. carboxylic acid)- Meta phenylene diamine. Yellow brown.

Aceto acetanilide Yellow.

13 Di(para-aminobenzoyl) 1:3-diamino benzene :(DKpera-aminebenzoyl) 3:5-diamino benzoylJ-acid); Beta naphthol Orange 20 14 Di(parawamino-benzoyl) 1:4-diamino benzene do Bordeaux. 15 Di(para-amino benzoyl) 1:4-diamino naphthalene :Kmetaremino-benzoyl) J-acid); Orange- 16 DKpara-aminmbenzoyl) 1:4-diamino naphthalene. 25

:Kpara-amino-benzoyl) J-acid):

17 Di(para-amino-benzoyl) 1:4-diamino naphthalene Beta mpmhol Do 3(l-meta-amino-phenyl-5-pyrazolone-3-carboxylic acid): l-phenyl-3-methyl-5-pyrazolone Yellow. Beta naphthol Orange.

18 Di(pera-ammo-benzoyl) 1:3-diammo benzene+sulfome acid ii-zlfhydgoxyoumolmen YBHJOJW. 30

-- ce 0 ace amhde o. eee p mze m bphenywmethybwmm m tolylene diemine.-. Yellow brown. 19 Di(par a-e.mino-benzoyl 1:3-dmmmo benzenmnllome acid jametg-amind-benzoyl') 1mm. naphtha orange- 20 Di(pera-emino-benzoyl) lzi -diemino benzene--sulfonlc acid v :(wa-anfino-benzoyl) J-acld); 35

. Beta naphthol Orange. 21 Di(p|ara-amino-benzoy1) 1:3-diamin0benzene-4au1fonicaciikphtenyl-%-!:PY1-5-DYI8ZO1OD8- Yellgw. ce 0 ace e 1 e o. ,(l-meta-ammo-p e ylet y py eh tmihydmxy quinoline eta phenylene diamine Yellow brown. 22 Di(para-amino-benzoyl) 1:3-d1emino benzene+sulfonie eeid 40 (1-mete-emino-phenyl-5-pyrazolone-3-carboxylic acid) ((para-amlno- Beta naphthol. Orange. benzoyl) .T-acid) 23 Di(pare.-amino-benzoyl) lzHliemmo benzeae i-sulfomc new...

:(meta toluidi 24 Di(pare-amino-benzoyl) 1:3-diamino benzene-Bulimia mid; :(DKpara-aminobenzoyl) 3:5-diamino benzoyl .T-aoid); 45

25 Di(para-amlno-bemoyl) 1:3-diamino benzene--sullonie Bold:-

gunman am,-no benzoyl) 3zmamimbemoyl mid -p y t y -fi-py o e Yellow Orange- 26 Di(para-amino benzoyl)- Lvi-dieminobenzene-fi-sulionie acid.--

:Kpam-amino-benzoyl) I-acid): Betanaphthol Omnge' 27 I Di(pare-amino-benzoyl) 1 :4-dia.min.o benzene-G-sultonie acidd 50 :gqmeta-amino-benzoyl) J-acidh. 28 D i( pa.ra-amin0-:Denz0y1) lz4-diamino benzene5-sullomz acid Bata naphthol (1-meta-emmo-phenyl-5-pyrazolone-3-catboxy11c acid); l-phenyl-3-rnethyl-5-pyrazolone Yellow. 29 Di(pa.ra-amino-henzoyl) lzi diamino benzene-5-su1lonic acid Beta napmhol Orange. (l-meta-emino-pl1enyl-3-methyl-5-pyraz0lone)L l-phenyl-3-meth'yl-5-pyrazolone Yellow. 55

3o. Di(pam-emino-benzoyl) 1:4-diamino benzene-eslllionic acid Beta nephthol Z Bordeaux.

a 31 Di(meta-amino-benzoy1)l:S-diamino benzene-4-sulfon1o 801d 3((mete-amino-benzoyl) J-acid): orange 32 DKmeta-amino-benzoyl) 1:3diamino benzene-4-sulfonlc acid. 60

' ('(para-amino-benzoyl) J-acid):

I Beta naphtha] Orange. 33 Di(mete.-aminobenzoyl) 1:3-dxemmo benzene-4-sulfon1c 801d l-phenyl-Ii-methyl-5-pyrazo1one Yellow. 3(l-meta-amino-phenyl- -pyrazolone -carboxylic acid): igfiiggg ggffff 3:

Meta phenylene diamine Red brown. 5 Beta naphthol Orange.

34 Di(meta-ammo-benzoyl) 1:3-d1amxno henzene-i-eultonie acid bfez tolegene gla m menn mu geg brown. -p y -1ne y -pyrazo onee ow. ,(1-meta-a x p v fl e y py e): 2: Mihydmxy quinoline Amte acetanilide.. Do. 35 Di(para-emino-benzoy1) 1:3-d1ammo benzene-4-sulfomc acid Beta 0mm j 1-meta-amino-phenyl-5-pyrazolone-3-earboxylic acid): 1-phenyl3-methyl-5-pyrazolone Yellow.

a6 D i pam-amin emoyl) mi m Beta naphtha} Grimm 7o (l-meta-amino-pheny1-5-pytazolone-3 carboxyho acid): l-phenyl-3-methyl-epymzolone Yellow.

F. The. products of the invention may be nuclei in which coupling takes place ed- 15; produced on the fiber or in isolated form. Coujacent to an hydroxy or amino group. The

azo components are represented by the formula:

R2N=NR1-COHN R--NHOCR1--N=NR2 in which R comprises a benzene nucleus, R1 comprise aryl nuclei, and R2 comprise benzene, naphthalene or pyrazolone nuclei.

G. There may be substituted on the various nuclei of the invention substituent groups from the list alkyl, alkoxy, halogen, aryloxy, aralkyl, aralkoxy, aryl, hydroaryloxy, trifluoro-alky, hydroxy, sulfonic acid and carboxyl.

H. The preferred products, when applied by diazotization and development on the fiber, pro- I. As many apparently widely diiferent embodiments of this invention may be made without departing from the spirit and scope thereof, it is to be understood that I do not limit myself to the specific embodiments thereof except as defined in the appended claims.

I claim:

1. The compound represented by the formula:

duce dyeings of outstanding fastness to washing H i a,

and of exceptional discharge properties. The

dyes are frequently used in the form of their alkali metal salts.

3. The compound represented by the formula:

4. The compound represented by the formula:

5. A material of organic fibrous origin dyed with the product represented by the formula:

6. A material of organic fibrous origin'dyed thol sulfonic acid, 1-meta-amino-pheny1-5-pywith-the product represented by the formula: razo1one-3-methy1, and 1-meta-amino-pheny1-5- 7. A material of organic fibrous origin dyed pyrazo1one-3-carb oxy1, and Y is one of a group with the product represented by the formula: consisting of hydrogen and sulfonic acid.

in which each R is a radical of a. primary-arylamine of the group consisting of an amino naph- 8. material of organic fibrous origin dyed with the product represented by the formula:

SWANIE s. ROSSANDER.

Certificate of Correction February 21, 1939.

t t No. 2,148,134. Pa en SWANIE S. ROSSANDER It is hereby certified that error appe I numbered patent requiring correction as follows.

for :Di read 131), and that the said Letters correction therein that the same may conform to the recor igned and sealed this 18th day of April, A. D. 1939.

Henry Van Ar s de-1e- DAL] Acting Commissioner of Patents. 

